Process for supplying a gas, especially of diborane and silane

ABSTRACT

A process for supplying a gas to a reactor comprising the steps of: 
     (i) continuously measuring density of the gas, the gas including at least one component which is susceptible to formation of an undesired side product as shown by a variation in density of the gas; and 
     (ii) modifying feed conditions of the gas if formation of the undesired side product is shown by a variation in the density of the gas. 
     The process can be employed to continuously monitor the content of diborane (B 2  H 6 ) in a mixture with silane (SiH 4 ) in a process for producing a borophosphosilicate glass. 
     An apparatus for supplying a gas to a reactor is also disclosed.

BACKGROUND OF THE INVENTION

The present invention relates to the supplying of gas, such as a gaseous mixture based on diborane (B₂ H₆) and of silane (SiH₄), destined for a reactor for growing layers of glass having a base of boron, phosphate, silicate (BPSG) ("boro-phospho-silicate glass) beginning with an initial feed of B₂ H_(6/) SiH₄ in determined proportions.

It is known that this type of mixture is modified with time by virtue of the tendency of diborane (B₂ H₆) to be transformed to higher boranes, notably those such as tetraborane (B₄ H₁₀), pentaborane 11 (B₅ H₁₁) which, on one hand, release hydrogen (H₂) and, on the other hand, are sometimes transformed to a liquid or even solid form which is not transferred with the gaseous flow. As a result, even when starting from perfectly suitable starting materials, the mixture transferred to the reactor is of improper composition notably, the mixture being of lower boron content, which forestalls against proper growing of the BPSG glass layer. This is the reason that, currently, analyses of the gaseous mixture being transferred to the reactor are carried out such as by chromatography which is not very practical because such method is discontinuous and requires frequent recalibration.

SUMMARY AND OBJECTS OF THE INVENTION

The present invention has as its goal the perfecting of this measurement by substituting therefore a method of completely different type, which is particularly well adapted to the type of application discussed above and which is reliable, continuous, simple and by virtue of which there is permitted an immediate correction, in the event of a deviation in the measured value of the content of B₂ H₆ as compared to the consigned value.

These objects are attained, according to the invention, by continuously measuring the density of the gas or mixture and subsequently determining the variation of the composition, in particular of the content of B₂ H₆ in a manner such that, if necessary, the conditions of gaseous feeding of the gas or notably of the mixture (B₂ H₆) (SiH₄) (S₂) can be modified. The measurement of the density is preferably carried out by means of a gaseous density meter, of the type comprising a vibrating tube which is under the effect of electrical excitation, the frequency of the vibration depending on the density of the mixture crossing said vibrating tube, and then by processing the frequency information, optionally as a function of other information such as the pressure and temperature of the gaseous mixture, in order to continuously determine the value of the density of said mixture.

Information such as the density can be used in order to modify the conditions of feeding, particularly of the mixture B₂ H₆ -SiH₄, for example by controlling the flow of gas or the flow of the gaseous mixture and/or by combining it with a additional corrector flow stream, for example one having a diborane (B₂ H₆) base in combination with an inert gas.

The invention also relates to the implementation of this process.

It is noted that although the present method focusses primarily on a process wherein a diborane gas is fed to a reactor in order to produce a borophosphosilicate glass, it is equally applicable to other processes wherein a gaseous feedstock is susceptible to side reactions forming undesired side products, such side products causing a change in the density of the gas which can be monitored so that, if necessary, adjustments in the feed materials can be carded out.

Thus, in a first aspect, the present invention relates to a process for supplying a gas to a reactor comprising the steps of:

(i) continuously measuring the density of the gas, the gas including at least one component which is susceptible to formation of an undesired side product as shown by a variation in density of the gas; and

(ii) modifying feed conditions of the gas if formation of the undesired side product is shown by a variation in the density of the gas.

In a more preferred aspect, the present invention relates to a process for supplying a gas comprising a mixture of B₂ H₆ and SiH₄ to a reactor for growing layers of borophosphosilicate glass comprising the steps of:

(i) continuously measuring the density of the gas by (a) passing a stream of the gas across a vibrating tube under the effect of electrical excitation; and (b) measuring the density of the gas as a function of frequency of the vibrating tube, a variation in density of the gas being indicative of the formation of undesired side products of B₂ H₆ including higher boranes; and, if formation of higher boranes is shown by a variation in density of the gas,

(ii) modifying feed conditions of the gas.

In another aspect, the present invention relates to an apparatus for supplying a gas to a reactor comprising;

(i) a reservoir including a stock material which is a gas;

(ii) a reactor into which the gas is fed;

(iii) an input conduit between the stock material reservoir and the reactor, the input conduit being provided with a means for continuously measuring density of the gas, a variation in density of the gas being indicative of formation of an undesired side product in the gas; and

(iv) means for modifying feed conditions of the gas in response to formation of the undesired side product as shown by a variation in the density of the gas.

With the foregoing as well as other objects, advantages, and features of the invention that will become hereinafter apparent, the nature of the invention may be more clearly understood by reference to the following Detailed Description of Preferred Embodiments, the Figure, and the appended claims.

DESCRIPTION OF THE DRAWING

The FIG. depicts a cross-sectional view of the density meter of the invention as part of a schematic illustration of the overall process of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Below there is set forth in detail a preferred embodiment for carrying out the process in the reference drawing, which is now discussed in detail.

A conduit (1) links a reservoir of stock material (2) containing an initial gaseous mixture comprising diborane and silane to a utilization reactor (3). On the conduit (1) is mounted a gaseous density meter (10) having a frame (11) incorporating, between an intake (12) and an output (13), a vibrating tube (14) under the effect of an electrical excitation via a conductor (15), all of which are associated with a pressure gauge (16) and a temperature gauge (17). The gaseous density meter (10) including the vibrating tube (14) is commercially available from SARATOSA AUTOMATION. The precise type which has been used for the present invention is type FD 771 EBZT 4. It is noted that the supplier of such device provides the requisite information for determining density of a gas based on the frequency of vibration of the tube.

While the temperature and the pressure of the gaseous stream are advantageously continuously monitored, such measurement is not essential as there typically will not occur over the course of a process very wide variations therein. For this reason, it is the measurement of the density of the stream based on the frequency of vibration of the vibrating tube which is the most important measurement. The frequency of vibration of the tube (14) is displayed on a frequency meter (18), the information relating to frequency as well as that relating to pressure and temperature being processed in a processing unit (19) in order to calculate and display a density value and, if necessary, to in addition be transferred in a comparator (20) of the displayed value which is used to modify the opening of a valve (21) in the conduit (1), and/or open more or less the valve (22) controlling the flow of additional diborane starting from an auxiliary stock (23) of a mixture of diborane and inert gas (nitrogen, argon).

By way of example, there is given in the table below for a mixture B₂ H₆ /SiH₄ /H₂ the content in hydrogen (% H₂) determined starting from pressure readings (in bars), from temperature readings (° C.), and of measured frequency (μs) determining a density thus permitting calculation of the hydrogen content. It should be apparent that calculation of the hydrogen content permits calculation of the content of diborane in the mixture. These calculations can be carried out using classical thermodynamical concepts by relating, at given conditions of temperature and pressure, the density of the mixture to the partial densities of each component, taking into account data such as the constant of gases "R", the compressibility factors "Z" of each gas (that are given in tables as a function of pressure and temperature), and also the conversion factor "λ" of the decomposition reactions (λB₂ H₆ H₂) etc. For example, in the case of (SiH₄, B₂ H₆) as the original feed, one can designate the components as follows:

    ______________________________________                                                 Silane  α                                                                Diborane                                                                               β                                                                 Hydrogen                                                                               γ                                                        ______________________________________                                    

wherein α, β and γ are in volume and wherein α+β+γ=s. As the mixture changes, it is evidenced by a change in the density "ρ", the percent H₂ of this new mixture is as follows: ##EQU1## wherein λ=the conversion factor of the reaction (1<λ<3). ##EQU2## wherein ρ₀,SiH4, ρ₀,B2H6, and ρ₀,H2 represent the densities of each constituent at "normal" conditions (0° C., 1 attm.) and wherein Z_(i) represents the compressibility factors for each constituent and wherein R represents the gas constant.

It is the above correlation which enables the density calculated using the process of the invention to be used in determining how to adjust a feedstream, if necessary, due to transformation of the desired diborane feed into heavier non-desired boranes.

    __________________________________________________________________________          Pressure                                                                            Temperature                                                                           Frequency                                                                            Flow                                                                               Density                                             Hour bar  °C.                                                                            μs cc/min                                                                             B.sub.2 H.sub.6 /SiH.sub.4 /H.sub.2                                                    % H.sub.2-                                  __________________________________________________________________________     07:02:13                                                                            3.352                                                                               18.6   373.3318                                                                             199.5                                                                              1.420213                                                                               .7990299                                    07:03:39                                                                            3.353                                                                               18.6   373.3384                                                                             199.5                                                                              1.419841                                                                               .8267524                                    07:05:04                                                                            3.361                                                                               18.6   373.3621                                                                             199.4                                                                              1.419879                                                                               .8238842                                    07:06:31                                                                            3.354                                                                               18.6   373.3465                                                                             199.4                                                                              1.419862                                                                               .8251541                                    07:07:56                                                                            3.353                                                                               18.6   373.3474                                                                             199.5                                                                              1.420088                                                                               .8083447                                    07:09:22                                                                            3.361                                                                               18.6   373.3694                                                                             199.4                                                                              1.420316                                                                               .7913489                                    07:10:48                                                                            3.35 18.7   373.3328                                                                             199.4                                                                              1.420167                                                                               .8024486                                    07:12:14                                                                            3.353                                                                               18.7   373.3368                                                                             199.4                                                                              1.420599                                                                               .7703218                                    07:13:41                                                                            3.356                                                                               18.7   373.3415                                                                             199.4                                                                              1.42063 .7680131                                    07:15:06                                                                            3.353                                                                               18.7   373.3402                                                                             199.4                                                                              1.42018 .8014629                                    07:16:32                                                                            3.35 18.7   373.3314                                                                             199.4                                                                              1.420238                                                                               .7972096                                    07:17:58                                                                            3.354                                                                               18.7   373.336                                                                              199.4                                                                              1.420184                                                                               .8011966                                    07:19:24                                                                            3.35 18.7   373.3373                                                                             199.4                                                                              1.420401                                                                               .7850533                                    07:20:50                                                                            3.352                                                                               18.7   373.3374                                                                             199.4                                                                              1.420518                                                                               .7763334                                    07:22:16                                                                            3.349                                                                               18.7   373.3308                                                                             199.4                                                                              1.420447                                                                               .7815724                                    07:23:42                                                                            3.352                                                                               18.7   373.328                                                                              199.5                                                                              1.420415                                                                               .7839788                                    07:25:08                                                                            3.345                                                                               18.7   373.3081                                                                             199.5                                                                              1.420134                                                                               .804926                                     07:26:34                                                                            3.348                                                                               18.7   373.3202                                                                             199.5                                                                              1.420195                                                                               .800353                                     07:27:59                                                                            3.347                                                                               18.7   373.3164                                                                             199.4                                                                              1.420172                                                                               .8021111                                    07:29:25                                                                            3.345                                                                               18.7   373.3018                                                                             199.4                                                                              1.420145                                                                               .8040913                                    07:30:52                                                                            3.343                                                                               18.7   373.3015                                                                             202.2                                                                              1.420177                                                                               .8017116                                    07:32:17                                                                            3.348                                                                               18.7   373.309                                                                              199.4                                                                              1.420302                                                                               .7923879                                    07:33:43                                                                            3.344                                                                               18.8   373.3008                                                                             199.4                                                                              1.420213                                                                               .7990122                                    07:35:09                                                                            3.34 18.8   373.2899                                                                             199.4                                                                              1.420393                                                                               .7856215                                    07:36:35                                                                            3.336                                                                               18.8   373.2789                                                                             199.4                                                                              1.420628                                                                               .7681285                                    07:38:01                                                                            3.337                                                                               18.8   373.2755                                                                             199.4                                                                              1.420274                                                                               .794519                                     07:39:27                                                                            3.338                                                                               18.8   373.2745                                                                             199.4                                                                              1.420701                                                                               .7627208                                    07:40:53                                                                            3.337                                                                               18.8   373.2733                                                                             199.4                                                                              1.420268                                                                               .7949275                                    07:42:19                                                                            3.337                                                                               18.8   373.2708                                                                             199.4                                                                              1.420457                                                                               .7808532                                    07:43:44                                                                            3.334                                                                               18.8   373.2673                                                                             199.4                                                                              1.420311                                                                               .7917485                                    07:45:11                                                                            3.335                                                                               18.8   373.2741                                                                             199.4                                                                              1.42041 .7843606                                    07:46:37                                                                            3.338                                                                               18.8   373.2753                                                                             199.4                                                                              1.420066                                                                               .8099786                                    07:48:02                                                                            3.342                                                                               18.8   373.2851                                                                             199.4                                                                              1.420515                                                                               .7765376                                    07:49:28                                                                            3.332                                                                               18.8   373.2645                                                                             199.4                                                                              1.420063                                                                               .8102361                                    07:50:54                                                                            3.333                                                                               18.8   373.2585                                                                             199.4                                                                              1.420448                                                                               .7815546                                    07:52:20                                                                            3.329                                                                               18.8   373.2497                                                                             199.4                                                                              1.420441                                                                               .7820608                                    07:53:46                                                                            3.332                                                                               18.8   373.2585                                                                             199.5                                                                              1.420482                                                                               .7789707                                    07:55:12                                                                            3.332                                                                               18.8   373.2602                                                                             199.4                                                                              1.420282                                                                               .7939063                                    07:56:38                                                                            3.33 18.8   373.2485                                                                             199.4                                                                              1.420051                                                                               .811133                                     07:58:04                                                                            3.329                                                                               18.9   373.2466                                                                             199.5                                                                              1.420538                                                                               .7748504                                    07:59:30                                                                            3.332                                                                               18.9   373.2489                                                                             199.4                                                                              1.420727                                                                               .7607139                                    08:00:56                                                                            3.327                                                                               18.9   373.2392                                                                             199.4                                                                              1.420414                                                                               .7840853                                    08:02:22                                                                            3.328                                                                               18.9   373.2387                                                                             199.4                                                                              1.420523                                                                               .7759693                                    08:03:48                                                                            3.328                                                                               18.9   373.2393                                                                             199.4                                                                              1.420513                                                                               .7766975                                    09:05:14                                                                            3.326                                                                               18.9   373.2292                                                                             199.4                                                                              1.420829                                                                               .7531573                                    08:06:40                                                                            3.324                                                                               18.9   373.2231                                                                             199.4                                                                              1.420798                                                                               .7554749                                    08:08:06                                                                            3.323                                                                               18.9   373.2176                                                                             199.4                                                                              1.42029 .7933025                                    08:09:32                                                                            3.319                                                                               18.9   373.2126                                                                             199.4                                                                              1.42031 .791784                                     08:10:58                                                                            3.322                                                                               18.9   373.2158                                                                             199.4                                                                              1.420668                                                                               .7651538                                    08:12:23                                                                            3.319                                                                               18.9   373.2078                                                                             199.5                                                                              1.420544                                                                               .7743798                                    08:13:49                                                                            3.322                                                                               18.9   373.2116                                                                             199.4                                                                              1.420047                                                                               .811426                                     08:15:16                                                                            3.319                                                                               18.9   373.2003                                                                             199.4                                                                              1.420154                                                                               .803452                                     08:16:41                                                                            3.317                                                                               18.9   373.1939                                                                             199.4                                                                              1.420165                                                                               .8026262                                    08:18:07                                                                            3.317                                                                               18.9   373.199                                                                              199.4                                                                              1.420003                                                                               .814676                                     08:19:33                                                                            3.319                                                                               18.9   373.2029                                                                             199.4                                                                              1.419958                                                                               .8180147                                    08:21:00                                                                            3.315                                                                               19     373.1924                                                                             199.4                                                                              1.420605                                                                               .7698156                                    08:22:26                                                                            3.315                                                                               19     373.1944                                                                             199.4                                                                              1.420534                                                                               .7750991                                    __________________________________________________________________________

Although only preferred embodiments have been specifically illustrated and described above, it will be appreciated that many modifications and variations of the invention are possible in view of the above teachings without deviating from the spirit and intended scope of the invention. 

What is claimed is:
 1. A process for supplying a gas to a reactor comprising the steps of:(i) continuously measuring density of the gas, said gas including at least one component which is susceptible to formation of an undesired side product as shown by a variation in density of said gas; and (ii) modifying feed conditions of said gas if formation of the undesired side product is shown by a variation in the density of said gas.
 2. The process according to claim 1 wherein said component susceptible to formation of an undesired side product is diborane (B₂ H₆).
 3. The process according to claim 1 wherein the step of measuring the density of the gas further comprises the steps of:(i) passing a stream of said gas across a vibrating tube under the effect of electrical excitation; and (ii) measuring the density of said gas as a function of frequency of said vibrating tube.
 4. The process according to claim 2 wherein the gas supplied to the reactor comprises a mixture of B₂ H₆ and SiH₄.
 5. The process according to claim 4 wherein the B₂ H₆ and SiH₄ are present in amounts effective for growing layers of borophosphosilicate glass.
 6. The process according to claim 4 wherein the undesired side product is a higher borane including tetraborane (Bhd 4H₁₀) and/or pentaborane 11 (B₅ H₁₁).
 7. The process according to claim 3 wherein the step of measuring the density of the gas further comprises, in addition to measuring the frequency of the vibration of said tube, the steps of measuring pressure, temperature, or both of the gas.
 8. The process according to claim 4 wherein said step of modifying the feed conditions of said gas further comprises modifying feeding conditions of the mixture of B₂ H₆ and SiH₄.
 9. The process according to claim 8 wherein the feeding conditions for the mixture of B₂ H₆ and SiH₄ are modified by controlling the flow of the gas and/or by combining the gas with an additional correcting stream having a base of B₂ H₆.
 10. A process for supplying a gas comprising a mixture of B₂ H₆ and SiH₄ to a reactor for growing layers of borophosphosilicate glass comprising the steps of:(i) continuously measuring the density of the gas by (a) passing a stream of said gas across a vibrating tube under the effect of electrical excitation; and (b) measuring the density of said gas as a function of frequency of said vibrating tube, a variation in density of said gas being indicative of the formation of undesired side products of B₂ H₆ including higher boranes; and, if formation of higher boranes is shown by a variation in density of said gas, (ii) modifying feed conditions of said gas.
 11. The process according to claim 1, wherein said undesired side product is a gaseous side product. 